EP2462182A2 - Agglomerated particulate lignosulfonate - Google Patents
Agglomerated particulate lignosulfonateInfo
- Publication number
- EP2462182A2 EP2462182A2 EP10768060A EP10768060A EP2462182A2 EP 2462182 A2 EP2462182 A2 EP 2462182A2 EP 10768060 A EP10768060 A EP 10768060A EP 10768060 A EP10768060 A EP 10768060A EP 2462182 A2 EP2462182 A2 EP 2462182A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- lignosulfonate
- granules
- cement
- average size
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 114
- 239000008187 granular material Substances 0.000 claims abstract description 82
- 239000004568 cement Substances 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 29
- 239000011859 microparticle Substances 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003129 oil well Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011236 particulate material Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011398 Portland cement Substances 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 3
- 239000011575 calcium Substances 0.000 claims 3
- 229910052791 calcium Inorganic materials 0.000 claims 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 2
- 238000005507 spraying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 39
- 238000009826 distribution Methods 0.000 description 14
- 239000007921 spray Substances 0.000 description 12
- 229920005551 calcium lignosulfonate Polymers 0.000 description 8
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012615 aggregate Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229920005550 ammonium lignosulfonate Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- -1 melamine sulfonates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/111—Aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/12—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone characterised by the shape, e.g. perforated strips
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- This invention relates to lignosulfonates.
- Lignosulfonates are produced in large quantities as a byproduct of the pulp and paper industry, and have a number of valuable industrial uses. Lignosulfonates normally are used in their as-produced liquid form. Spray drying has been employed to convert the liquid to a finely-divided powder, and some end-users employ the resulting powder rather than the liquid. Lignosulfonate powder has also been mixed with lignosulfonate liquid to form a paste, then ground and sieved.
- Liquid lignosulfonates include a substantial amount of water.
- the water content increases the product weight, volume and shipping cost and may be an undesirable component or diluent for some end uses.
- Spray-dried lignosulfonates typically include an appreciable portion of very small dusty particles. Grinding a dried lignosulfonate paste can consume appreciable time and energy, and can yield a product having a broad range of particle sizes including an appreciable portion of very small dusty particles.
- the present invention provides in one aspect a method for making a particulate material, which method comprises:
- the invention provides in another aspect a particulate material comprising non- comminuted lignosulfonate granules having an average size of at least 0.1 mm.
- the invention provides in a further aspect a method for making a cement additive comprising dry-blending cement powder with non-comminuted lignosulfonate granules having an average size of at least 0.1 mm.
- the invention provides in yet another aspect a cement additive comprising a mixture of cement powder and non-comminuted lignosulfonate granules having an average size of at least 0.1 mm.
- the invention provides in yet another aspect a concrete mixture or oil well cement comprising a blend of cement, water, non-comminuted lignosulfonate granules having an average size of at least 0.1 mm and optional aggregate or proppant.
- the disclosed lignosulfonate granules may provide one or more advantages such as low manufacturing cost, dustless or near-dustless dispensing characteristics, desirable handling and storage characteristics, low hydroscopicity and rapid aqueous dissolution.
- FIG. 1 is a schematic view of one embodiment of the disclosed manufacturing method
- FIG. 2 is a schematic view of another embodiment of the disclosed
- Fig. 3 is a graph showing particle size distribution data for a spray-dried lignosulfonate powder and nine non-comminuted lignosulfonate granule samples;
- Fig. 4 is a graph showing particle size distribution data for a
- Fig. 5 is a graph comparing concrete workability as a function of time for the Fig. 4 calcium lignosulfonate granule samples and for a spray-dried lignosulfonate powder made from the same calcium lignosulfonate;
- Fig. 6 is a graph showing particle size distribution data for three non- comminuted calcium lignosulfonate granule samples.
- cement additive that contains "a” lignosulfonate material may include “one or more” lignosulfonate materials.
- average size when used in respect to a collection of particles means the smallest sieve opening (expressed in mm) that will retain 50 wt. % of the particles in the collection using the measurement procedure described in Example 1.
- the term "comminuted" when used in respect to a particulate material means that the particles have been fractured and reduced in size while dry by cutting, grinding, pulverizing, triturating or other particle fracturing process employing externally-applied forces significantly greater than the modest particle fracturing forces which may be experienced by particles travelling though a fluidized bed agglomerator.
- dry when used in respect to a particulate material means that the particles do not include visible moisture and are free-flowing when poured.
- granules means a collection of particles whose average size is at least 0.1 mm.
- lignosulfonate includes sulfonated lignin, sulfite lignin reaction products, and spent sulfite liquors that may be further reacted, purified, fractionated or the like to produce lignosulfonate-containing materials of interest.
- microparticles means a collection of particles whose average size is less than 0.1 mm.
- the term "Portland cement” includes pure Portland cement as well as blended cements containing Portland cement and a cement extender (e.g., blast furnace slag, or fly ash and other pozzolans).
- a cement extender e.g., blast furnace slag, or fly ash and other pozzolans.
- size when used in respect to a particle means the smallest sieve opening (expressed in mm) that will enable the particle to pass through the sieve using the measurement procedure described in Example 1.
- the recitation of a numerical range using endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).
- the recitation of sets of upper and lower endpoints e.g., at least 1, at least 2, at least 3, and less than 10, less than 5 and less than 4) includes all ranges that may be formed from such endpoints (e.g., 1 to 10, 1 to 5, 2 to 10, 2 to 5, etc.).
- Fig. 1 shows an exemplary schematic view of one embodiment of the disclosed manufacturing method.
- Continuous fluid bed agglomerator 100 includes a housing 102 containing fluidized bed 104.
- Lignosulfonate microparticles 106 may be introduced into fluidized bed 104 through inlet chute 108 (e.g., as a spray-dried lignosulfonate powder), may be formed in fluidized bed 104 by adding lignosulfonate liquid 110 to fluidized bed 104, e.g., through spray nozzle 112 or other suitable injector, or may be both introduced and formed in fluidized bed 104.
- Heated gas streams such as streams 114, 116, 118 and 120 (e.g., of heated air) may be introduced into fluidized bed 104 through supply chambers 122, 124, 126 and 128 and distribution plate 130.
- Additional lignosulfonate liquid 110 may be introduced into fluidized bed 104 via spray nozzles or other suitable injectors such as spray nozzles 132 and 134. Exposure to the heated gas and liquid lignosulfonate in the agglomerator will cause the lignosulfonate microparticles to agglomerate, grow or otherwise enlarge in size.
- Spent process gas such as gas streams 136, 138 may be removed from expansion zone 140 as filtered gas stream 142 by passage through filters such as filters 144, 146, 148, 150, 152, 154, 156 and 158 mounted in filter support plate 160.
- Lignosulfonate granules 162 may be removed from fluidized bed 104 through outlet chute 164. Microparticles and undersized agglomerates may be separated from the granules 162 (using for example, air classification) and returned to inlet chute 108 for further agglomeration or growth in fluidized bed 104, and the remaining lignosulfonate granules may be collected and used in various product applications.
- Fig. 2 shows an exemplary schematic view of another embodiment of the disclosed manufacturing method.
- Batch fluid bed agglomerator 200 includes a housing 202 containing fluidized bed 204. Lignosulfonate microparticles 206 may be introduced into fluidized bed 204 through inlet pipes 208, 210.
- Heated gas streams such as streams 212, 214, 216 and 218 (e.g., of heated air) may be introduced into fluidized bed 204 through supply pipes 220, 222 and distribution plate 224. Additional lignosulfonate liquid 226 may be introduced into fluidized bed 204 via spray nozzles or other suitable injectors such as spray nozzle 228. Exposure to the heated gas and liquid lignosulfonate in the agglomerator will cause the lignosulfonate microparticles to agglomerate, grow or otherwise enlarge in size.
- Spent process gas such as gas streams 230, 232 may be removed from expansion zone 234. Lignosulfonate granules 236 may be removed from fluidized bed 204 through outlet pipe 238.
- Microparticles and undersized agglomerates may be separated from the granules 236 (using for example, air classification) and employed in or in place of the stream of lignosulfonate microparticles 206 when the next lignosulfonate agglomerate batch is prepared in apparatus 200.
- the remaining lignosulfonate granules may be collected and used in various product applications.
- a variety of apparatus configurations and process parameters may be employed in an apparatus like that shown in Fig. 1 or Fig. 2.
- a top spray lignosulfonate application may be employed in the Fig. 1 apparatus or a bottom spray lignosulfonate application may be employed in the Fig. 2 apparatus.
- a stream of lignosulfonate microparticles may be introduced at the start of operating a continuous agglomeration apparatus like that shown in Fig. 1 and then switched off, with the apparatus thereafter being operated using only lignosulfonate liquid introduction.
- Process parameters including the introduction rates for lignosulfonate microparticles, lignosulfonate liquid and heated gas; the overall or localized gas stream and bed temperatures; and other parameters which will be appreciated by persons having ordinary skill in the art of fluidized bed agglomeration may be adjusted or otherwise altered to control the rate and extent of microparticle agglomeration, growth or other enlargement.
- the heated gas stream temperatures for continuous fluidized bed agglomerator operation may be about 170 to about 250° C or about 170 to about 210° C
- the bed temperatures for continuous fluidized bed agglomerator operation may be about 60 to about 80° C.
- Bed retention times may for example be less than two hours, less than one hour, or about 15 to about 45 minutes.
- the bed temperatures, bed retention times and other conditions are such that the lignosulfonate granules undergo the desired degree of enlargement without becoming significantly oxidized or otherwise unduly degraded.
- the proportion of lignosulfonate microparticles used to make the desired lignosulfonate granules having an average size of at least 0.1 mm may for example represent 0 to about 40 or about 1 to about 35 wt. % of the collected granules.
- lignosulfonate liquid used to make such granules may for example represent 100 to about 60 or about 99 to about 65 wt. % of the collected granules.
- a variety of lignosulfonates may be employed to make the disclosed granules.
- Exemplary lignosulfonates may be obtained from a variety of sources including
- the lignosulfonates may be utilized in crude or pure forms, e.g., in an "as is" or whole liquor condition, or in a purified lignosulfonate form from which or in which sugars and other saccharide constituents have been removed or destroyed, or from which or in which inorganic constituents have been partially or fully eliminated.
- the lignosulfonates may be utilized in salt forms including calcium lignosulfonates, sodium lignosulfonates, ammonium lignosulfonates, potassium lignosulfonates, magnesium lignosulfonates and mixtures or blends thereof.
- Lignosulfonates are available from a number of suppliers including Borregaard LignoTech, Georgia-Pacific Corporation, Lenzing AG and Tembec Inc.
- a variety of fluid bed agglomerators may be employed to make the disclosed granules.
- Exemplary agglomerators include those shown or described in U.S. Patent Nos. 3,913,847 (Glatt et al.) and 6,740,632 Bl (Jacob et al.).
- Other fluidized bed agglomerators are available from commercial suppliers including Glatt Air Techniques, Inc. and Niro, Inc.
- the disclosed granules may also be prepared by modifying a fluidized bed dryer to spray or otherwise add liquid lignosulfonate to heated lignosulfonate particles.
- a lignosulfonate liquid spray could be added to the fluidized bed lignosulfonate powder reactor described in U.S. Patent No. 3,476,740 (Markham et al.) and the operating temperatures and residence times described therein could be reduced to limit or prevent lignosulfonate oxidation. The operating temperatures, residence times and spray liquid addition rates could then be adjusted to bring about lignosulfonate microparticle enlargement and the formation of lignosulfonate granules.
- the collected granules may consist of or consist essentially of lignosulfonate and may be coated or uncoated.
- the granules may for example have an average size of about 0.1 to about 10 mm, about 0.1 to about 5 mm, about 0.1 to about 2 mm, about 0.1 to about 1 mm, or about 0.1 to about 0.5 mm.
- the collected granules desirably contain little or no (e.g., less than 5 wt. %, less than 3 wt. % or less than 1 wt. %) particles having a size less than 0.1 mm.
- the granules also desirably have a higher density (for example, an uncompressed bulk density of about 550 to about 800 or about 560 to about 775 kg/m 3 ) than spray-dried powder made using the same lignosulfonate starting liquid.
- a higher density for example, an uncompressed bulk density of about 550 to about 800 or about 560 to about 775 kg/m 3
- spray-dried powder made using the same lignosulfonate starting liquid.
- the granules When moistened or otherwise exposed to water or humid conditions, the granules desirably exhibit slower moisture absorption, remain free-flowing at higher moisture contents or are less prone to lump formation than spray-dried powders made using the same
- the granules desirably also have reduced tendency to leak from packaging (e.g., paper sacks), emit little dust or substantially no dust when poured, have a reduced tendency to remain behind in packaging when poured, or are easily removed from a spill site if accidentally spilled.
- packaging e.g., paper sacks
- the disclosed lignosulfonate granules may be used in a variety of products and uses including cement additives, well cements (e.g., for gas, oil or water wells), pigment dispersants, battery separators, animal feeds and agricultural chemicals including the products or uses referred to in U.S. Patent Nos. 2,582,459 (Salathiel), 4,284,433
- the disclosed granules have particular value in cement additives and well cements, and can be provided in a dry particulate form which may be much more conveniently shipped, stored or dispensed than corresponding additives made using lignosulfonate liquids or microparticle powders (e.g., spray-dried powders).
- the granules desirably provide comparable or improved fluidity, water content, set time retardation or air entrainment compared to cement additives made from spray-dried lignosulfonate powders made from the same lignosulfonate starting liquid.
- Cement additives and well cements containing the granules may include a variety of adjuvants, for example other cement plasticizers and superplasticizers such as melamine sulfonates (MSF), naphthalene sulfonates (PNS), polycarboxylates and polycarboxylic ether (PCE) polymers.
- the total cement plasticizer or superplasticizer amount including any lignosulfonate which may be present, may for example be up to about 100 % of the cement weight employed in the final concrete or well cement mixture, but desirably provide desired property improvements at much lower addition levels, e.g., at about 0.1 to about 1 % solids based on the cement weight.
- De-foaming agents for example tri-n-butylphosphate (TBP) and tri-iso- butylphosphate (TiBP) may be employed, e.g., in amounts of about 0.1-0.2 wt. % based on the cement weight.
- TBP tri-n-butylphosphate
- TiBP tri-iso- butylphosphate
- a variety of biocides or other preservatives may be employed, including compounds which give off formaldehyde (at, e.g., about 0.1-0.2 wt. % based on the cement weight), phenolic compounds (at, e.g., about 0.2-0.5 wt. % based on the cement weight) and isothiazolinone preparations (at, e.g., about 0.02-0.2 wt. % based on the cement weight).
- the disclosed granules may be packaged without requiring biocides.
- Retarders for example sucrose, gluconates, phosphates (e.g., tetrapotassium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate) may be employed, e.g., in amounts of about 0.2-2 wt. % based on the cement weight.
- Accelerators for example silicates and salts thereof including the sodium or potassium salts, aluminates, carbonates, formiates, amorphous aluminum hydroxides and aluminum sulfate may be employed, e.g., in amounts of about 1-3 wt. % based on the cement weight.
- Air-entraining agents for example natural resins (e.g., resin soap, tall resins, colophony and other gum resins, and root resins) and synthetic non-ionic or ionic surfactants (e.g., akylpolyglycol ethers, alkylsulfates and alkylsulfonates) may be employed, e.g., in amounts of about 0.5-1 wt.
- Stabilizers and sedimentation reducers may also be employed, for example starch derivatives and other polysaccharides (e.g., cellulose ether, starch ether, xanthan gum and whelan gum), synthetic high molecular weight polymers (e.g., polyethylene oxides and polyacrylates) and fine grained inorganic substances with large specific surfaces (e.g., silica powder, silica suspensions and silica sols), e.g., in amounts up to about 1 wt. % based on the cement weight.
- starch derivatives and other polysaccharides e.g., cellulose ether, starch ether, xanthan gum and whelan gum
- synthetic high molecular weight polymers e.g., polyethylene oxides and polyacrylates
- fine grained inorganic substances with large specific surfaces e.g., silica powder, silica suspensions and silica sols
- the dry nature of the disclosed granules permits them to be used to make dry cement additives which may be combined with cement, aggregate and water to prepare concrete mixtures at reduced dilution compared to concrete mixtures made using liquid lignosulfonate additives.
- the disclosed granules also may be combined with cement, proppants and water to make oil well cements with desirable fluidity and curing characteristics.
- a continuous feed GLATTTM fluidized bed agglomerator equipped with sprayheads for bottom spray liquid introduction was employed to make a series of lignosulfonate granules.
- the agglomerator was initially operated using spray-dried lignosulfonate microparticles (made using BORRESPERSETM CA-SA lignosulfonate liquid from Borregaard LignoTech) as a seed feed, additional BORRESPERSE CA-SA lignosulfonate liquid in the bottom spray units as an agglomerating liquid feed, and process air heated to about 190° C.
- the seed and liquid feed streams were initially introduced in a 30:70 weight ratio.
- the agglomerator was operated at full capacity using a bed residence time of about 15-20 minutes, and at 50% capacity using a bed residence time of about 25-30 minutes.
- the microparticle feed could be switched off shortly after the start of each run and similar granules could be obtained by increasing the bed residence time to about 25-30 minutes for operation at full capacity and about 40-45 minutes for operation at 50% capacity.
- a series of 9 granule samples was prepared. Particle size distribution curves for these samples are identified in Fig. 3 as Curve B through Curve J, along with a comparison particle size distribution curve (Curve A) for the spray-dried lignosulfonate powder.
- Fig. 3 Particle size distribution curves for these samples are identified in Fig. 3 as Curve B through Curve J, along with a comparison particle size distribution curve (Curve A) for the spray-dried lignosulfonate powder.
- Fig. 3 Curve B through Curve J
- Sieves were used to measure particle size distributions for the Curve B through Curve J granule samples. The sieve measurement procedure employed approximately 200 g portions of the tested granules. The granules were poured over a stack of measurement sieves in graduated sizes and shaken for 5 minutes using a Model 1132-2- A sieve vibrator (from Pascall Engineering), followed by weighing to determine the granule weight in each sieve.
- Dry flow properties were evaluated by individually placing 200 g samples of each granule and of the Curve A powder in a 360 mm tall by 70 mm diameter vertical plastic cylinder whose lower end had been fitted with a plastic funnel.
- the funnel had a 22 mm diameter outlet placed 150 mm above a Model PG5002-S laboratory balance (from Mettler-Toledo).
- Flow curves were prepared by measuring the total sample weight under the funnel at one second intervals. Depending on the granule sample average particle size, the granules exited the funnel within 9-12 seconds after the start of measurement, with larger average particle size samples exiting more quickly than smaller average particle size samples.
- the Curve A powder sample remained in the cylinder and funnel and did not drop onto the balance.
- Aqueous dissolving speed was evaluated by individually placing sufficient amounts of each granule sample in deionized water to provide 45% or 50% dry matter in a 2Kg solution.
- the water was stirred in a 2 L beaker at approximately 550 rpm using a model RW 20 stirring motor (from Kanke & Kunkel) equipped with a two-bladed metal propeller.
- the sample was dropped onto the water all at once and a stopwatch was employed to measure the time required to obtain a uniformly dissolved mixture.
- the 45% dry matter solutions dissolved in 10 to 30 minutes, and the 50% dry matter solutions dissolved in 30 to 45 minutes.
- a 45% dry matter solution made using the Curve A spray-dried powder required 60 minutes to dissolve, and a 50% dry matter solution required 75 minutes to dissolve.
- Fig. 4 shows a particle size distribution curve (Curve K) for a comparison cement additive sold as TAMOLTM NH 7519 naphthalenesulphonic acid condensation product (from BASF) and three particle size distribution curves for fine (Curve L), medium (Curve M) and coarse (Curve N) granules made using BORRESPERSE CA calcium lignosulfonate.
- the horizontal axis in Fig. 4 shows the sieve opening in mm and is non-linear.
- the concrete mixtures were evaluated for air content, density, set time, initial slump and slump loss.
- the dry individual cement additives were also placed in a 1 L calibrated container and evaluated to determine their uncompacted bulk densities. The uncompacted samples were then vibrated for 30 seconds using a vibration table. The calibrated container was refilled and again vibrated for another 30 seconds and a density for the resulting compacted additive was recorded. The individual cement additives were also evaluated to determine wt. % dry matter.
- the results of the concrete mixture and additive evaluations are shown below in Table A. Slump loss results are also shown in Fig.
- FIG. 6 shows particle size distribution curves for the resulting fine (Curve S), medium (Curve T) and coarse (Curve U) granules.
- the horizontal axis in Fig. 6 shows the sieve opening in mm and is non-linear.
- the granules and a lignosulfonate powder made from spray-dried BORRESPERSE NA sodium lignosulfonate were used as cement additives at 0.30 % sbwc, and evaluated for air content, density, set time, initial slump and slump loss.
- the dry additives were also evaluated for uncompacted and compacted bulk densities and wt. % dry matter. The results are shown below in Table B.
- Table B Compared to the spray-dried lignosulfonate, the granulated lignosulfonates had slightly increased air content, lower initial slump, similar slump retention and similar set time.
- the spray-dried lignosulfonate powder formed considerable dust when poured, whereas no dusting was observed when pouring the granulated lignosulfonates.
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Abstract
Description
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US12/538,015 US8277557B2 (en) | 2009-08-07 | 2009-08-07 | Agglomerated particulate lignosulfonate |
PCT/IB2010/002185 WO2011015950A2 (en) | 2009-08-07 | 2010-08-06 | Agglomerated particulate lignosulfonate |
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EP2462182A2 true EP2462182A2 (en) | 2012-06-13 |
EP2462182B1 EP2462182B1 (en) | 2017-12-20 |
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EP (1) | EP2462182B1 (en) |
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CA2781093C (en) | 2009-12-16 | 2018-02-27 | Domsjoe Fabriker Ab | Lignosulfonate of a certain quality and method of preparation of lignosulfonate of a certain quality |
WO2013158219A1 (en) * | 2012-04-20 | 2013-10-24 | Empire Technology Development Llc | Cellulose hydrolysis via modified lignosulfonate catalysts |
WO2019235497A1 (en) * | 2018-06-04 | 2019-12-12 | 東亞合成株式会社 | Water repellent oil repellent film composition and use of same |
CN110615896B (en) * | 2019-09-04 | 2021-12-03 | 上海昶法新材料有限公司 | Method for preparing lignosulfonate water reducing agent from dissolving pulp pulping waste liquid |
US11155683B2 (en) * | 2019-09-13 | 2021-10-26 | Nanophase Technologies Corporation | Lipophillically dispersed phenolic polymer particles |
US20220181607A1 (en) * | 2020-12-03 | 2022-06-09 | University Of Wyoming | Carbon foams, doped carbon composites, processes for fabricating carbon foams and doped carbon composites, and uses thereof |
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- 2010-08-06 EP EP10768060.5A patent/EP2462182B1/en active Active
- 2010-08-06 WO PCT/IB2010/002185 patent/WO2011015950A2/en active Application Filing
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2012
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EP2462182B1 (en) | 2017-12-20 |
WO2011015950A2 (en) | 2011-02-10 |
US20130095319A1 (en) | 2013-04-18 |
US8946396B2 (en) | 2015-02-03 |
US8277557B2 (en) | 2012-10-02 |
ES2655726T3 (en) | 2018-02-21 |
US20110030587A1 (en) | 2011-02-10 |
US20150152229A1 (en) | 2015-06-04 |
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